Treatment of rosin with amines



Patented Sept. 4, 1945 august mna'mmr or nosnv amnvns u ns Alter, SouthOrange, N J.

v No Drawing. Application emu-125,10, 7 8erlalNo.473,547 q 9 Claims.(01. zoo-10s) This invention relates to treatment or rosin to modify theproperties thereof, the invention being especially concerned with atreatment precas -involving the use of certain aromatic amines or'aromatic amino-compounds,'of types set out more fully hereinafter. Theinvention also is concerned with improved modified rosin productsproduced by treatment with aminocompounds. k

The present application is a continuation-in part of my copendingapplication Serial No.- 888,049, filed March 12, 1941, issuedas Patent2,809,088. January 28, 1943. I i Various rosin materials constitute avaluable source of raw materials fora number of purposes, for instance,in the plastics and coating composition industries. The invention isconcerned with the modification of the propertiesofrosinsoastobetterilttherosinforusein various industries such as thosementioned above. For instance, it is contemplated that treatmentaccording to this invention may alter and improve variouscharacteristics not only of the rosin itself but also of coatingscontaining such treated rosin products, for example, water resistance,alkali resistance, solubility, etc.

Briefly described, involves heating the rosin in the presence of theamino-compound selected, the treatmentbeing continued for. the timerequired to bring about the desired modihcations. Before considering theprocess in detail, reference is now made to the amino-compounds hereincontemplated foruse. r

Treating went According to the invention, aromatic monoprimary amines,or substitution products thereof,

homologues and their derivatives, and also salts of the amines orsubstitution products maybe employed. These amino-compounds may berepresented by the general formula given below, and hereinafteridentified as general Formula 1.

radical. 7

Moreover, the invention is particularly concerned with amino-compoundsof the class which may be represented by the following general formula,hereinafter identified as general Formula II.

xs-R-NH: where V where R=grouping containing .at least iaryl Here againit may be mentioned that'the compounds coming within the general-formulamay also be usedin theform of their salts;

Examples of mono-primary amines coming within the scope of generalFormula II- are: Beta-naphthylamine Alpha-naphthylamlne In'the foregoinggeneral II, it is to be understood that the term ary "is usedto identifythe aromatic ring plus hydrogen atoms. ltxamples of various, complexlamina-com pounds, forv instance, substituted mono-amines, coming withinthe scope of general Formula II are as follows: a

i-chloro-o-anisidine Bodium2:6:8 naphthylamine disulphonate Sodium1:8:3:6 aminonaphthol disulphonate ap thv amine sulphonic acid Y2:lnaphthylamine:sulphonic acid.v I Y Beta-naphthylamine 3:648trisulphonic acid, m-Xylidin sulphonic acid p-Toluidine m--sulphonicacid m-Nitroaniline hydrochloride Amlno-azo-benrene Amino-azo-bensenesulphate Trichloraniline hydrochloride, DlnitroanilineAmlnosalicylicacid m Naphthylamines also Y containing sulphonic,-,hy-'droxy, and other substltuent groups. An example of a, complex mixedamino-compound coming'wlthin the scope mula I is: eurhodine. I

From the above it will be seen that quite a wide variety of aromaticmen-primary aminocompoundsmay be employed. Salts of amines and also ofsubstitution products thereof also of many different types, as be appreelated.

Various of the classes of compounds whichr'nay be employed, and also.v'ariousindividual compounds, yield somewhat different' characteristicsin the treated product, sothat selectionof the modifying agent shouldbe-made in accordance with thepropertiesdeslre'd in the product. It maybe mentioned that, as "compared with certain other aromaticamino-compounds, many of the primary amines are capable of producing'aproduct having somewhat lower acid value. Main, as "compared withcertain other aminocompounds, the mono-amines are frequently of especialadvantage where it is desired ,toincrease v the solubility ofthe'product. f

Although the treated rosinproducts of the present invention haveadvantageous properties when employed in varnishes or invarnishbases,'such products may also be employed for many other purposes.

'NII,ornjcefgr ii e l Use of the expression varnish base" herein, 1means all or part of the varnish solids, i. e., all 9-01 part of thefilm forming ingredients of the varnish base. Such varnish bases ortheir dispersions; (for instance. solutions) may, of course,

I be employed either clear or pigmented. 'Usually the varnish basecontains both the resinous ingredient and a fatty oil ingredient, forexample,

1 drying or semi-drying fatty oils.

With regard to the action of the modifying Supplemental treating agentsmay be present during the reaction, among which might be mentioneddissolution promoting agents of the type described in my issued PatentNo. 2,293,038.

Some more or less general considerations regarding the process shouldbe'noted. as follows: Although the complete mechanism of modificationmay not'be fully understood, it may be agents. it should further bementioned that many of the amino-compounds contemplated for useincorporate a variety of different groups, radicals, 1 etc.. so that inthe case of various complex amino-compounds the product is modified incertainrespects by virtueof the presence of onel group ,or'radical, andin other respects by virtue of the presence of another group or radical.

Thus composite or compound effects may be secured.

Treatment conditions with regard to treatment conditions it may be notedthat anywhere from a trace, for instance .1 %fof the amino-compound uptoabout 10% is'usually found satisfactory, from .about 2% to about 5%normally yielding good results. For special purposes'larger amounts maybe used, for instance up toabout 30%.

The temperature of treatment should be within a range extending fromabout-l00 C- to about 350 C. but not above the point atwhich appreciabledestructive distillation of the rosin will take place. Usuallytemperatures from to 310 C. are employed.

The time of treatment atthe reaction temperature may be varied over aconsiderable range although the time usuallyyneed not be more than a fewhours, for instance from about 1 hour to about 5 hours is requireds, Insome cases modifibatch may be permitted to cool almost immedi ately uponattaining thedesired treatment tem-v perature.

Frequently the reaction of air may be'brought aboutby blanketi'ng the:

surface of the reaction mixture with some inert gas, such as 80%, CO2,or nitrogen, or by bubbling such gases through the mass. Where vacuumisused, a pressure, for instance, of about 100 mms. Hg to about 450 mms.Hg will'be'found effective, although higher or lowermay be used. Vacuumserves to take-off volatile reaction products. for instance, water, ifany .is formed. Whatever means or procedure is employed, in many casesit is of advantage to so conduct the process as to reduce oxygeneoncentration'i'n the reaction vessel and prevent entrance of fresh'airoroxygen to the reaction mixture.

Various gases may be employed for their supplemental effect during thetreatment procedure and -gases for various purposes may either beemployed as a blanket on the surface of the batch undergoing treatmentor may be bubbled through the reaction mixture.

about 200 C.

is desirably carried out in the absenceofair, or out of contact with anycation is brought about quite rapidly and the? ,In considering thestarting material on which the process-may be employed, it is firstnoted that the process brings about changes both of a colloidal and alsoof .achemical nature. It is important. however, to bear in mind that theprocess essentially involves a reaction with the rosin molecule, thatis, with the type of molecules of which the basic constituents ofnatural rosin are composed. Therefore, while rosin itself, such as gumor wood rosins, represents perhaps the most important starting materialto which the process is adaptable, it is noted that the process may beemployed on rosin which has been pretreated in various ways, or on mixedor chemically condensed materials incorporating rosin, since thereaction will take place wherever the rosin molecule ispresent provided.of course, that the physical or chemical state or .environment' of therosin molecule is-not such as to prevent the reaction from taking place.

It may also. be mentioned that there are other natural resins, suchas,,copals, which act simi- Oil larly to rosin by treatment inaccordance with this invention. In fact, the reaction may be carried outon any of the natural resins containing high'molecular resinacids-Therefore, wherever any such other natural resin behaves similarly torosin, it is herein considered as an equivalent.

Copals are fossil gums which have to be fused" before becoming solublein organic solvents and miscible with fatty oil. When copals are used inthe present process. they should be employed in the fused state.

'The modifiedproduct of this invention may if desired, be subject toother treatment, depending upon the use forwhich it is intended. ,Thus,for example, the modified products may be vulcanized with sulfur. Themodified resin products secured in accordance with the foregoing, may bevulcanized as such, by application of heat, or in solutions, such asvarnish solutions (inthe latter case with sulfur chloride).

In the examples given below, melting point determinations were made bythe Mercury method,

and iodine value determinations were made by the Wiis method.

Exnlrnss Example ,1

A batch of 300 grams of rosin was heatedin a Direct heating was applied,raising the temperature to from 290 to 310' 0., which temperature wasmaintained for about hours. During the treatment a vacuum pressure of 8to 17 inches of mercury was employed, 1. e., 8 to 17 inches pressurereduction from atmospheric. About 20 minutes were required to, reachabout 292' C. and dissolution of the modifying agent occurred about 20minutes after reaching that temperature.

The product was a relatively soft golden brown solid displaying onlyvery little darkening as com- D red with the untreated material.

Comparative Examples 2 to 4 In the following examples the treatmentconditions were similar in each case. In each example WW wood rosin(Newport Industries) was employed as the starting material, this rosinhaving the following characteristics:

Acid number 186.4 Baponiflcatlon No 172 Iodine number 192.2 Meltingpoint 'C 82.0

Example 2 The modifying agent employed in this example wa 4 amino 1,3dimethylbenune. The yield was about 97% and the product was of verylight color, having the following haracteristics:

Acid number 124.5 Baponiflcation No 136.5 Iodin number 162.8 Meltingpoint C 77.5

Although the amine compound here employed contains some substitutions,the substituents are of such character as not to materially influencethe properties of the product, so that the modification of propertieswas in at least major part due to the amine groups of the compound. Thisis in contrast with Examples 3 and 4 below, wherein certain of thesubstituents present materially influenced the properties of theproduct,

beyond or differently from the modifications very light color, havingcharacteristics as follows:

Acid number 122.0 Saponiilcation No 133 Iodine number 154.1 Meltingpoint C.. 66.5

Still another composite action shows up in this example. The haloportion of the compound apparently influenced the melting point,eflecting an appreciable reduction, as will be seen from comparison withthe melting point of the untreated material (820 C.)

I claim:

1. A process for modifying the properties of rosin comprising heatingthe rosin to a temperature between about 100 C. and about 310 C. in

the presence of from about 0.1% to about 10% or an aromaticamino-compound selected from the class consisting of amino-compoundshaving the following general formula, and salts thereof:

Xa-R-NHI wher R=at least 1 aryl radical =A substituent of the classconsisting of nitro-, sulfo-, halo-, alkyl-, aryl-. aralkyl-, acyl-,aracyl-. hydroxy, CHOH, carboxy, SH, CN, CO, CB and S0 radicals, and andoxygen 2. A process in accordance with claim 1 in which the treatmenttemperatureis at least about 3. A process in accordance with claim 1 inwhich the quantity of amino-compound is between about 2% and about 5% ofthe rosin.

4. A modified rosin comprising rosin reacted 40 with from about .1% toabout 10% of an aromatic brought about by the amine groups of thecompounds there used.

Example 3 In this example the modifying agent was m-nitro aniline.

During the treatment, when the temperature had passed about 200 C., thematerial became of a dark brownish-yellow color. The yield was 95.4%.Characteristics of this product were as follows:

Acid number 118.5 Baponiilcation No 122 Iodine number 150.8 Meltingpoint C 91.5

Here it will be noted that an appreciable increase in melting point isshown, apparently because of the nitro-group in the compound.

Example I In this example the modifying ent was 2,4 dichloroaniline.

. rosin comprising heating mono-primary amino-compound.

5. A process for modifying the properties of rosin comprising heatingthe rosin to a temperature between about C. and 310 C. in the presenceof from 0.1% to about 10% of betanaphthylamine.

6. A process for modifying the properties of rosin comprising heatingthe rosin to a tempera-' which R is one benzene radical and a is atleast 1.

LAszLo AUER.

, 3" The yield here was 09.5%. the productbeing of CH0, aso, sulfurabout 10% of a naph-

